Preparation method of hydrophilic / hydrophobic double-layer nanofiber membrane with full degradability
The preparation of fully biodegradable hydrophilic/hydrophobic bilayer nanofiber membranes by electrospinning technology solves the problems of poor biodegradability and functional limitations of traditional nanofiber membranes, and realizes multifunctionality and wide range of biological applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NANJING TECH UNIV
- Filing Date
- 2024-12-26
- Publication Date
- 2026-05-19
AI Technical Summary
Traditional nanofiber membranes have poor biodegradability and are difficult to balance with hydrophilicity, which limits their application in the biological field.
A fully biodegradable hydrophilic/hydrophobic bilayer nanofiber membrane was prepared using electrospinning technology. By selecting appropriate polymer materials and carbon dots (CDs), the composition and structure of the hydrophilic and hydrophobic layers were controlled, thereby achieving multifunctionality of the membrane material.
The prepared nanofiber membranes have excellent biodegradability, antibacterial and anti-inflammatory properties, making them suitable for promoting wound healing and repairing the urethral lining, thus expanding their application scope.
Smart Images
Figure CN119711050B_ABST
Abstract
Description
Technical Field
[0001] This invention specifically relates to the preparation of an electrospun nanofiber membrane, and particularly to a hydrophilic / hydrophobic bilayer electrospun nanofiber membrane with fully degradable properties, belonging to the field of novel bio-nanomaterial preparation. Background Technology
[0002] Nanofibers, as a novel high-performance material, possess high specific surface area, abundant pore structure, and excellent mechanical properties, making them a popular choice in many application fields. In recent years, nanofiber membranes have been widely used in water treatment, air filtration, tissue engineering, drug delivery, sensors, and environmental remediation. Electrospinning technology, in particular, has become one of the main methods for preparing nanofiber membranes due to its ability to produce fibers with diameters ranging from nanometers to micrometers. While traditional nanofiber membranes possess micrometer-scale fiber diameters and excellent mechanical properties, they often suffer from poor biodegradability. Furthermore, traditional nanofiber membranes also have limitations in functionalization; for example, it is difficult to achieve a balance between hydrophilicity and hydrophobicity in a single-material nanofiber membrane structure, affecting the overall performance and lifespan of the membrane material. Based on this, this invention proposes a bilayer nanofiber membrane design scheme. By controlling the composition and structure of the two layers, composite functions such as hydrophilicity and hydrophobicity can be achieved in the membrane material. Furthermore, by employing highly biocompatible degradable materials, its biodegradability can be improved, demonstrating promising application prospects in the biological field.
[0003] Hydrophilic / hydrophobic bilayer nanofiber membranes, by designing a two-layer structure with both hydrophilic and hydrophobic materials, can simultaneously meet multiple needs in different scenarios. For example, the hydrophobic layer can improve the waterproofness of the nanofiber membrane, while the hydrophilic layer helps to enhance its adsorption capacity. The hydrophilic / hydrophobic bilayer structure allows for flexible adjustment of the physical properties of the nanofiber membrane according to actual needs, expanding its applicability in various applications.
[0004] This invention aims to achieve multifunctionality and optimized degradability of nanofiber membranes by rationally selecting biodegradable polymer materials. A hydrophilic / hydrophobic bilayer nanofiber membrane with fully biodegradable properties is prepared using electrospinning technology, meeting both biodegradation requirements and possessing strong application value. Furthermore, the addition of carbon dots (CDs) endows the hydrophilic layer with excellent antibacterial and anti-inflammatory properties. By selecting an appropriate spinning solution ratio, a reasonable combination of hydrophilic and hydrophobic layers can be achieved, thereby endowing the nanofiber membrane material with multiple functions. This meets the needs of biological fields such as promoting the healing of superficial skin wounds and repairing wounds on the urethral wall, and has broad market prospects and application potential. Summary of the Invention
[0005] This invention provides a method for preparing a fully biodegradable hydrophilic / hydrophobic bilayer nanofiber membrane by electrospinning, which addresses the need for biofunctional applications of nanofiber membrane materials in the prior art. The invention also discloses the selection and adjustment of the prepared fully biodegradable hydrophilic / hydrophobic bilayer nanofiber membrane to give it good application prospects.
[0006] Based on this, the present invention provides a method for preparing a fully degradable hydrophilic / hydrophobic bilayer nanofiber membrane by electrospinning. The specific steps are as follows:
[0007] Step 1: Dissolve polylactic acid-glycolic acid copolymer (PLGA), polyethylene glycol monomethyl ether (mPEG) and carbon dots (CDs) uniformly in hexafluoroisopropanol, and stir with a magnetic stirrer until a uniform pale yellow solution is obtained, which is used as the spinning solution for the hydrophilic layer.
[0008] Step 2: Dissolve polycaprolactone (PCL) uniformly in hexafluoroisopropanol and stir with a magnetic stirrer until completely dissolved into a transparent solution, which will be used as the spinning solution for the hydrophobic layer.
[0009] Step 3: Using the solution from Step 1 as the spinning solution, electrospin the hydrophilic nanofiber membrane using an electrospinning machine;
[0010] Step 4: Using the solution from Step 2 as the spinning solution, electrospinning of the hydrophobic nanofiber membrane is carried out on the basis of the hydrophilic nanofiber membrane from Step 3, and finally a hydrophilic / hydrophobic bilayer nanofiber membrane is obtained.
[0011] Furthermore, in step 1, CDs were prepared using polyethyleneimine (PEI), citric acid, and glutathione as raw materials, and dissolved in hexafluoroisopropanol for later use, with a concentration of 0.15 g / mL.
[0012] Furthermore, in step 1, the molecular weight of mPEG is 1000–4000 g / mol.
[0013] Furthermore, in step 1, the amount of PLGA added is 0.75–1.5 g, the amount of mPEG added is 0.25–0.6 g, the amount of the organic solvent hexafluoroisopropanol is 4.5–10 mL, and the amount of CDs added is 0.5–1 mL.
[0014] Furthermore, in step 2, the amount of PCL added is 0.8–1.8 g, and the amount of the organic solvent hexafluoroisopropanol is 6.6–13.2 g;
[0015] The spinning solution with hydrophilic and hydrophobic layers was obtained using the preparation method described above.
[0016] The hydrophilic and hydrophobic spinning solutions are used to prepare a fully biodegradable hydrophilic / hydrophobic bilayer nanofiber membrane using an electrospinning machine.
[0017] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0018] In this invention, the addition of mPEG enhances the hydrophilicity of the hydrophilic layer, while the addition of CDs enhances the antioxidant properties of the hydrophilic nanofiber membrane, demonstrating its potential application in wound dressings. Furthermore, both the hydrophobic and hydrophilic organic solvents are hexafluoroisopropanol, facilitating a more rational combination of the hydrophilic / hydrophobic bilayer nanofiber membrane. Based on electrospinning, the solution is electrospinned under high voltage to form a nanofiber membrane. The nanofibers possess high specific surface area and porosity, allowing carbon dots to adhere uniformly to the fiber surface, preventing aggregation and facilitating the effective utilization of carbon dots in various applications.
[0019] This invention provides a hydrophilic / hydrophobic bilayer nanofiber membrane that ensures uniform adhesion of carbon dots to the hydrophilic layer. The hydrophilic layer, due to the inclusion of carbon dots (CDs), contributes to antioxidant and wound healing properties, while the hydrophobic layer helps isolate the wound from the external environment, preserving the function of the CDs in the hydrophilic layer. This nanofiber membrane is a fully biodegradable material and can also be used for antibacterial, anti-inflammatory, and wound healing applications in areas such as the urethra. Through mass production of fully biodegradable hydrophilic / hydrophobic bilayer nanofiber membranes, it can be applied in the biomedical field. Attached Figure Description
[0020] Figure 1 A schematic diagram of the water contact angle on the surface of the hydrophobic nanofiber membrane prepared by electrospinning in Example Case 6.
[0021] Figure 2 A schematic diagram of the water contact angle on the surface of the hydrophilic nanofiber membrane prepared by electrospinning in Example Case 6.
[0022] Figure 3 A scanning electron microscope (SEM) schematic diagram of the surface morphology of the hydrophobic nanofiber membrane prepared by electrospinning in Example 6.
[0023] Figure 4 A scanning electron microscope (SEM) schematic diagram of the surface morphology of the hydrophilic nanofiber membrane prepared by electrospinning in Example 6.
[0024] Specific implementation examples
[0025] The present invention will now be described in detail and clearly. While the described examples are only a portion of the examples and do not represent all examples, they will enable those skilled in the art to gain a deep understanding of the advantages and features of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
[0026] Unless otherwise specified, the experimental methods described below are conventional; unless otherwise specified, the raw materials and reagents described below are commercially available.
[0027] Example 1
[0028] Step 1: Weigh 1.5g PLGA and 0.6g mPEG with a molecular weight of 1000g / mol; continue to measure 10mL hexafluoroisopropanol and 1mL CDs, and stir with a magnetic stirrer until completely dissolved to obtain a uniform pale yellow solution.
[0029] Step 2: Weigh 0.8g of PCL with a molecular weight of 80000g / mol, and weigh 9.2g of hexafluoroisopropanol. Stir with a magnetic stirrer until a homogeneous and transparent solution is obtained.
[0030] Step 3: Using the solution from Step 1 as the hydrophilic layer spinning solution, synthesize a hydrophilic layer nanofiber membrane using an electrospinning machine;
[0031] Step 4: Using the solution in Step 2 as the hydrophobic layer spinning solution, synthesize a hydrophobic layer nanofiber membrane based on the hydrophilic layer nanofiber membrane in Step 3 using an electrospinning machine.
[0032] The hydrophilic nanofiber membrane prepared in this example has a contact angle of 27°, and the hydrophobic nanofiber membrane has a contact angle of 101°.
[0033] Example 2
[0034] Step 1: Weigh 1.5g PLGA and 0.6g mPEG with a molecular weight of 1000g / mol; continue to measure 10mL hexafluoroisopropanol and 1mL CDs, and stir with a magnetic stirrer until completely dissolved to obtain a uniform pale yellow solution.
[0035] Step 2: Weigh 1.6g of PCL with a molecular weight of 80000g / mol, and weigh 18.4g of hexafluoroisopropanol. Stir with a magnetic stirrer until a uniform and transparent solution is obtained.
[0036] Step 3: Using the solution from Step 2 as the hydrophobic layer spinning solution, synthesize a hydrophobic nanofiber membrane using an electrospinning machine;
[0037] Step 4: Using the solution from Step 1 as the hydrophilic layer spinning solution, continue electrospinning to synthesize a hydrophilic layer nanofiber membrane based on the hydrophobic layer nanofiber membrane from Step 3.
[0038] The hydrophilic nanofiber membrane prepared in this example has a contact angle of 27°, and the hydrophobic nanofiber membrane has a contact angle of 101°.
[0039] Example 3
[0040] Step 1: Weigh 1.5g PLGA and 0.5g mPEG with a molecular weight of 1000g / mol; continue to measure 9mL hexafluoroisopropanol and 1mL CDs, and stir with a magnetic stirrer until completely dissolved to obtain a uniform pale yellow solution.
[0041] Step 2: Weigh 1.8g of PCL with a molecular weight of 80000g / mol, and continue to weigh 13.2g of hexafluoroisopropanol. Stir with a magnetic stirrer until a uniform and transparent solution is obtained.
[0042] Step 3: Using the solution from Step 2 as the hydrophobic layer spinning solution, synthesize a hydrophobic nanofiber membrane using an electrospinning machine;
[0043] Step 4: Using the solution from Step 1 as the hydrophilic layer spinning solution, continue electrospinning to synthesize a hydrophilic layer nanofiber membrane based on the hydrophobic layer nanofiber membrane from Step 3.
[0044] The hydrophilic nanofiber membrane prepared in this example has a contact angle of 22°, and the hydrophobic nanofiber membrane has a contact angle of 101°.
[0045] Example 4
[0046] Step 1: Weigh 1.5g PLGA and 0.5g mPEG with a molecular weight of 4000g / mol; continue to measure 5mL hexafluoroisopropanol and 1mL CDs, and stir with a magnetic stirrer until completely dissolved to obtain a uniform pale yellow solution.
[0047] Step 2: Weigh 1.8g of PCL with a molecular weight of 80000g / mol, and weigh 13.2g of hexafluoroisopropanol. Stir with a magnetic stirrer until a uniform and transparent solution is obtained.
[0048] Step 3: Using the solution from Step 1 as the hydrophilic layer spinning solution, synthesize a hydrophilic layer nanofiber membrane using an electrospinning machine;
[0049] Step 4: Using the solution in Step 2 as the hydrophobic layer spinning solution, synthesize a hydrophobic layer nanofiber membrane based on the hydrophilic layer nanofiber membrane in Step 3 using an electrospinning machine.
[0050] The hydrophilic nanofiber membrane prepared in this example has a contact angle of 17°, and the hydrophobic nanofiber membrane has a contact angle of 101°.
[0051] Example 5
[0052] Step 1: Weigh 1.5g PLGA and 0.5g mPEG with a molecular weight of 4000g / mol; continue to measure 6mL hexafluoroisopropanol and 1mL CDs, and stir with a magnetic stirrer until completely dissolved to obtain a uniform pale yellow solution;
[0053] Step 2: Weigh 0.9g of PCL with a molecular weight of 80000g / mol, weigh 6.6g of hexafluoroisopropanol, and stir with a magnetic stirrer until a uniform and transparent solution is obtained;
[0054] Step 3: Using the solution from Step 1 as the hydrophilic layer spinning solution, synthesize a nanofiber membrane with a hydrophilic layer by electrospinning.
[0055] Step 4: Using the solution in Step 2 as the hydrophobic layer spinning solution, synthesize a hydrophobic layer nanofiber membrane based on the hydrophilic layer nanofiber membrane in Step 3 using an electrospinning machine.
[0056] The hydrophilic nanofiber membrane prepared in this example has a contact angle of 30°, and the hydrophobic nanofiber membrane has a contact angle of 101°.
[0057] Example 6
[0058] Step 1: Weigh 1.5g PLGA and 0.5g mPEG with a molecular weight of 4000g / mol; continue to measure 6mL hexafluoroisopropanol and 1mL CDs, and stir with a magnetic stirrer for 4-5 hours until completely dissolved to obtain a uniform pale yellow solution.
[0059] Step 2: Weigh 0.9g of PCL with a molecular weight of 80000g / mol, weigh 6.6g of hexafluoroisopropanol, and stir with a magnetic stirrer for 5-6 hours until a uniform and transparent solution is obtained;
[0060] Step 3: Using the solution from Step 1 as the hydrophilic layer spinning solution, synthesize a hydrophilic layer nanofiber membrane with CDs by electrospinning.
[0061] Step 4: Using the solution in Step 2 as the hydrophobic layer spinning solution, synthesize the hydrophobic layer nanofiber membrane by electrospinning at the flow rate set in Step 3 and based on the hydrophilic layer nanofiber membrane with CDs.
[0062] The hydrophilic nanofiber membrane prepared in this example has a contact angle of 41°, and the hydrophobic nanofiber membrane has a contact angle of 101°.
[0063] Example 7
[0064] Step 1: Weigh 0.75g PLGA and 0.25g mPEG with a molecular weight of 4000g / mol; continue to measure 4.5mL hexafluoroisopropanol and 0.5mL CDs, and stir with a magnetic stirrer until completely dissolved to obtain a uniform pale yellow solution.
[0065] Step 2: Weigh 1.8g of PCL with a molecular weight of 80000g / mol, and weigh 13.2g of hexafluoroisopropanol. Stir with a magnetic stirrer until a uniform and transparent solution is obtained.
[0066] Step 3: Using the solution from Step 1 as the hydrophilic layer spinning solution, synthesize a hydrophilic layer nanofiber membrane using an electrospinning machine;
[0067] Step 4: Using the solution in Step 2 as the hydrophobic layer spinning solution, synthesize a hydrophobic layer nanofiber membrane based on the hydrophilic layer nanofiber membrane in Step 3 using an electrospinning machine.
[0068] The hydrophilic nanofiber membrane prepared in this example has a contact angle of 54°, and the hydrophobic nanofiber membrane has a contact angle of 101°. Characterization tests were performed on the hydrophilic / hydrophobic nanofiber membrane samples from Example 6, and the results showed that:
[0069] Please see Figure 1 , Figure 1 The diagram shows the surface water contact angle of the hydrophobic layer electrospun nanofiber membrane sample prepared in Example 6. As can be seen from the figure, the contact angle of the hydrophobic layer is 101°.
[0070] Please see Figure 2 , Figure 2 The diagram shows the surface water contact angle of the hydrophilic layer electrospun nanofiber membrane sample prepared in Example 6. As can be seen from the diagram, the contact angle of the hydrophilic layer is 41°.
[0071] Please see Figure 3 , Figure 3 The image shows a scanning electron microscope (SEM) schematic diagram of the surface morphology of the hydrophobic electrospun nanofiber membrane sample prepared in Example 6. As can be seen from the image, the nanofiber surface is smooth and uniformly distributed.
[0072] Please see Figure 4 , Figure 4 The image shows a scanning electron microscope (SEM) schematic diagram of the surface morphology of the hydrophilic electrospun nanofiber membrane sample prepared in Example 6. As can be seen from the image, the nanofiber surface is smooth and uniformly distributed.
[0073] The above results demonstrate that the fully biodegradable hydrophilic / hydrophobic bilayer nanofiber membrane of the present invention was successfully prepared by electrospinning. The addition of carbon quantum dots improves the antibacterial and anti-inflammatory properties of the nanofiber membrane, and the addition of the superhydrophilic precursor improves the hydrophilicity of the hydrophilic layer. Therefore, the preparation of the fully biodegradable bilayer nanofiber membrane can be applied in the biomedical field to promote wound healing.
[0074] Although the embodiments of the present invention have been disclosed above, their application is not limited to the specification and implementation methods. It can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention does not limit specific details.
Claims
1. A method for preparing a hydrophilic / hydrophobic bilayer nanofiber membrane with fully biodegradable properties, characterized in that, Includes the following steps: Step 1: Dissolve polylactic acid-glycolic acid copolymer, polyethylene glycol monomethyl ether, and carbon dots uniformly in hexafluoroisopropanol, and stir with a magnetic stirrer until a homogeneous pale yellow solution is obtained. This solution is used as the spinning solution for the hydrophilic layer. The carbon dots are prepared from polyethyleneimine, citric acid, and glutathione, and dissolved in hexafluoroisopropanol at a concentration of 0.15 g / mL. The amount of hexafluoroisopropanol added is 4.5–10 mL, the amount of polylactic acid-glycolic acid copolymer added is 0.75–1.5 g, the amount of polyethylene glycol monomethyl ether added is 0.25–0.6 g, and the amount of carbon dots added is 0.5–1 mL. Step 2: Dissolve polycaprolactone uniformly in hexafluoroisopropanol and stir magnetically until completely dissolved to obtain a transparent solution, which is used as the spinning solution for the hydrophobic layer; Step 3: Using the solution from Step 1 as the hydrophilic layer spinning solution, electrospinning is performed using an electrospinning machine to obtain a hydrophilic layer nanofiber membrane. Step 4: Using the solution from Step 2 as the hydrophobic layer spinning solution, electrospinning of the hydrophobic layer nanofiber membrane is carried out on the basis of the hydrophilic layer nanofiber membrane from Step 3, finally obtaining a hydrophilic / hydrophobic bilayer nanofiber membrane.
2. The preparation method according to claim 1, characterized in that, The molecular weight of the polyethylene glycol monomethyl ether mentioned in step 1 is 1000-4000 g / mol.
3. The preparation method according to claim 1, characterized in that, In step 2, the amount of polycaprolactone added is 0.8–1.8 g, and the amount of hexafluoroisopropanol added is 6.6–13.2 g.
4. The preparation method according to claim 1, characterized in that, The contact angle of the hydrophilic nanofiber membrane in step 3 is 17–54°, and the contact angle of the hydrophobic nanofiber membrane in step 4 is 101°.